Light-sensitive silver halide color-photographic material containing naphthal color couplers

ABSTRACT

WHEREIN X is hydrogen, halogen, sulfonic or sulfonate groups, Y is -(CH2)3-or -CH2-CH(CH3)-and R is an aliphatic hydrocarbon radical of eight to twenty carbon atoms. Light-sensitive silver halide color-photographic emulsions comprising cyan couplers of the formula:

United States Patent [72] lsabro Inoue;

Shui Sato; Yutaka Takei, all of Tokyo, Japan Mar. 19, 1968 Oct. 26, 1971Konishiroku Photo Industry Co., Ltd. Tokyo, Japan Mar. 22, 1967 JapanInventors App]. No. Filed Patented Assignee Priority U.S.(l V M 96/100Int. Cl G03c 1/40 Field of Search 96/100, 55

[5 6] References Cited UNITED STATES PATENTS 3,135,609 6/1964 Klinger96/100 Primary Examiner-J. Travis Brown AnorneyWaters, Roditi, Schwartz& Nissen ABSTRACT: Light-sensitive silver halide color-photographicemulsions comprising cyan couplers of the formula:

I p X wherein X is hydrogen, halogen, sulfonic or sulfonate groups, Y is-(CH,) -or Cl-l CH(Cl-l;,)-and R is an aliphatic hydrocarbon radical ofeight to twenty carbon atoms.

LIGHT-SENSITIVE SILVER HALIDE COLOR- PHOTOGRAPHIC MATERIAL CONTAININGNAPHTHAL COLOR COUPLERS This invention relates to a light-sensitivesilver halide colorphotographic emulsion capable of forming acyan-colored image, which comprises a novel cyan coupler of the formulawherein X is hydrogen atom,thalogen atom or a sulfonic or sulfonategroup, Y is (CH -orCH CH(Cl-l and R is an aliphatic hydrocarbon radicalof eight to 20 carbon atoms.

As a conventional cyan coupler usable for a light-sensitivecolor-photographic material positive material including acolor-photographic printing paper and a transparent photographicpositive there are known l-hydroxy-Z-naphthoalkyl amide derivativeswhich, for example, have any one of the following structures:

CONHCnHgr I S03N8 (PB Report F 546) A color-photographic material inwhich the above-mentioned coupler '[l] or [ll] is incorporated has manyadvantages, e.g. high photographic speed and maximum color densityobtained by the usual color development, and good spectral absorptioncharacteristics of cyan-colored images. Further, it is relatively freefrom staining of unexposed areas. However, the said material is stillnot entirely satisfactory because the resulting cyan-colored imagevaries in its density depending on the pH of a developing bath and thetime of water-washing during color development. Further, the color imageis sensible to light, heat and humidity so that it may be changed orfaded out in color during storage. This is a disadvantage when the saidmaterial is intended for use as photographic positive.

The present invention provides a light'sensitive silver halidecolor-photographic material which does not suffer from theabove-mentioned disadvantages.

The coupler of the above-indicated structural formula which is usablefor the present invention is a new compound whose structuralcharacteristic is that a cyan coupler component is connected through a C-alkylene chain by an amide linkage with a diffusion-inhibitingcomponent which includes a water-solubilizing group. Such compounds maybe prepared by using phenyl-l-hydroxy-Z-naphthoate propylenediamine,long chain alkyl succinic anhydride, etc.

Typical couplers which are suitably used in the present inventioninclude the following:

AOaNB CONE-CHr-CH -CHy-NHC O-GH -CH-C H15 4 O OH As is apparent fromthese structural formula, the coupler compounds of the present inventioncontain three carbon atoms in the alkylene chain linking the cyancoupler component and the diffusion-inhibiting component. ln contrast tothis, the conventionally known cyan couplers which are known have atmost two carbon atoms in the corresponding alkylene chain, as shown, forexample, by the following structuralfonnula Such a conventionally knowncoupler as [lll] is not free from the aforementioned defects. Foradditional information, a corresponding cyan coupler having a C-alkylene chain is synthesized only by using expensive startingmaterials. Another corresponding coupler having a C -aIkylene chain isdifficult to be synthesized. These should be construed as support, forpatentability of new cyan couplers used in this invention.

The following examples will serve to show the preparation of some newcyan couplers used in this invention.

SYNTHESIS OF COMPOUND (1) 53 g. of phenyll -hydroxy-2-naphthoate areadded to a solu- 5 tion of 45 g. of 1,3-propane diamine in 200 ml. ofacetonitrile at a temperature below C. After stirring the resultingmixture for 2 hours, the formed precipitate is collected by filtrationand recrystallized from n-butyl alcohol. N-(3-aminopropyl)-l-hydroxy-2-naphthoamide (intermediate product) melting atl83-l 84 C. is obtained as white crystalline needles. This intermediateproduct (12 g.) is heated together with 18 g. of n-octadecyl succinicanhydride and 60 ml. of glacial acetic acid at 70-80 C. for 15 minutes.The resulting reaction mixture is cooled to room temperature and theformed precipitate is collected by filtration and washed with glacialacetic acid and then with acetone and dried. Recrystallization fromApercent alcohol yields a white powder melting at l l5l 16 C. Thiscorresponds to compound l SYNTHESIS OF COMPOUND (3) In a similar mannerto thatfor obtaining the intermediate product in the synthesis ofcompound (1), phenyl-l-hydroxy- 4-chloro-2-napthoate is reacted withl,3-propane diamine. N-(3-aminopropyl)-l-hydroxy-4-chloro-2-naphthoamide (intermediate product)melting at 190 C. is obtained. The intermediate product is reacted withn-dodecyl succinic anhydride under the same condition as mentioned inthe synthesis of compound (1), thereby to yield compound (3) melting atlO4-l06 C.

SYNTHESIS OF COMPOUND (4) In the process for obtaining the intennediateproduct of the compound (1), l,2-propane diamine is used in place of1,3- propane diamine to give N-(2-methyl-2-aminoethyl)-l-2- naphthoamidemelting at 231 C. (intermediate product). The intermediate product isreacted with n-octyl succinic anhydride under the same condition asmentioned in the synthesis of compound (1), thereby to yield compound(4) melting at I 80-1 8 1 C.

SYNTHESIS OF COMPOUND (5) In a similar manner to that for obtaining theintermediate product of compound (1), phenyl-l-hydroxy-4-chloro-2-naphthoate is reacted with l,2-propane diamine. N-(Z-methyl-2-aminoethyl)- l -hydroxy-4-chloro-2-naphthoamide (intermediate product)melting at 227-228 C. is obtained. This intermediate product is reactedwith n-hexadecyl succinic anhydride under the same condition asmentioned in the synthesis of compound (1), thereby to yield compound(5) melting at 140-142 C.

SYNTHESIS OF COMPOUND (2) For 3 hours, 59 g. of compound (1) and 240 ml.of acetic acid are boiled. The mixture is then allowed to cool at roomtemperature and the precipitate formed is collected by filtration andwashed with methyl alcohol and dried. Recrystallization from 500 ml. ofethyl alcohol yields N-[3- (n-octadecylsuccinimido)propyl]-l-hydroxy-2-naphthoamide melting at 87-88 C.(intermediate product). 7

This intermediate product (58 g.) is suspended in 500 ml. ofacetonitrile and, to this suspension, 35 ml. of chlorosulfonic acid areadded in one batch at 20 C. while stirring. The temperature of thesuspension rises to 4550 C. and crystals are dissolved therein. Afterallowing to stand at room temperature, the precipitate formed isfiltered off. The filtered precipitate is washed two times with 100 ml.of acetonitrile and dried. The product is then dissolved in a mixture of300 ml. of N-caustic soda aqueous solution and 300 ml. of methylalcohol, and the resulting solution is made acidic with acetic acid. Theprecipitate formed is filtered off and washed with 50 percent methanoland dried. The compound (2) melting at l69-l74 C. is obtained as a whitepowder.

SYNTHESIS OF COMPOUND (6) Calculated Found Compound 0 H N C II N Thedata relating to the compounds (2) and (6) are those obtained from thecorresponding monohydrates, respectively.

The coupler compound thus prepared is dissolved in an aqueous alkalihydroxide or alkali carbonate solution or in an aqueous alcohol solutionand then the resulting solution is dispersed in a light-sensitive silverhalide color-photographic emulsion, which in turn is coated on anappropriate support, e.g. photographic film base or baryta paper, andthen dried, to thereby produce a light-sensitive color-photographicmaterial. The coupler content of the silver halide emulsion may varydepending on the type of the emulsion and molecular weight of thecoupler, but it should preferably be within the range of from 0.017moles to 0.l47 moles per mole of the silver halide present.

Any color developer which is commonly used for development ofconventional color-photographic materials is usable for thecolor-photographic material of this invention. For example,N,N-diethyl-p-phenylenediamine,N-ethyl-N-hydroxyethyl-p-phenylenediamine, N-ethyl-N-hydroxyethyl-Z-methyl-p-phenylenediaminc, N,N-diethyl-2-methyl-p-phenylenediamine,N-ethyl-N-B-methanesulfonamidoethyl-3- methyl-4-aminoaniline, etc., andtheir sulfates, sulfites or hydrochlorides are suitable colordevelopers.

A light-sensitive color-photographic material which contains a cyancoupler of the present invention has high photographic sensitivity evenby usual color development. Further, it has good spectral absorptioncharacteristics for photographic positives because the absorptionmaximum of the resulting cyan-colored image exists at around 690 mu.Still another advantage is the stability of color image densityirrespective of variation in the pH of the treating bath and the time ofwater-washing during color development. The resulting color image isquite stable against heat, light and humidity and so it can be preservedfor a long period of time.

The present invention is further illustrated by the following exampleswhich are not intended to limit the scope of the present invention:

EXAMPLE 1 In 30 ml. of N-potassium hydroxide solution, 8.0 g. of thecoupler compound (3) are dissolved and the solution is diluted withwater to ml. The resulting solution is added to 1 kg. of a red-sensitivesilver chloride emulsion and the mixture is adjusted to pH 6.7 with anaqueous citric acid solution.

The resulting emulsion is coated on a baryta paper and dried. Thelight-sensitive material thus prepared is exposed to light and thentreated at 20 C. for minutes in a developing bath having the followingformulation:

N-Ethyl-N-hydroxyethyl-p-phenylenediamine sulfate 2.5 g. Anhydroussodium sulfite 2.0 g. Hydroxylamine hydrochloride 1.0 g. Sodiumcarbonate (monohydrate) 82.0 g.

Potassium bromide 2.

Water to make up 1,000 ml.

Immediately after dipping in a stopping bath which comprises 10 ml. ofglacial acetic acid, 3.0 g. of caustic soda and 1,000 ml. of water, thelight-sensitive material is dipped in an acidic hardening fixing bathfor 4 minutes. The developed light-sensitive material is washed withwater for 10 minutes and subsequently treated at C. for 8 minutes in ableaching bath having the following formulation:

Sodium ethylenediamine tetraacetate 40 g. Ferric chloride g. Sodiumcarbonate (monohydrate) 20 g. Potassium bromide 30 g. Sodium thiosulfate200 5.

Water to make up L000 ml.

The bleached product is washed with water for 20 minutes and then dippedin a stabilizing bath for 2 minutes and dried. Cyan colored image havingan absorption maximum of 690 mp. is obtained.

Fading properties of the cyan-colored image obtained from the couplercompound (3) of this invention and the cyan-' colored images obtainedfrom the known couplers [I], [II] and [III] were tested. Thecyan-colored images obtained from the known cyan couplers [I], [II] and [III]by the similar treatment as above were used as controls. The fadingratio of the colored images after standing at 50 C. for 7 days under 80percent of relative humidity and the fading ratio after standing at C.for 4 days in Fade O-meter are shown in the table 1 below.

Table l Fading Ratio (Residual color density percent to l00% oforiginalcolor image density) Under 80% of relative humidity at 50 C. for ByFade-o-meter Cyan Coupler 7 days (k) Compound (3) of 98 94 thisinvention Known compound [l] 52 80 Known compound [II] 60 8| Knowncompound [ill] 65 80 As is apparent from table 1, the color images ofthe photographic materials containing the cyan couplers of the presentinvention are excellent in fastness against light, heat and humidity.Further, the image density of the cyan-colored image obtained by usingcompound (3) is stable, irrespective of the pH of the treating bath andthe time of water-washing.

EXAMPLE 2 10 minutes with a developing solution of the followingformulation:

Methol 3 g. Anhydrous sodium sulfite 60 g. Hydroquinone 6 g. Anhydroussodium carbonate 50 g.

Potassium bromide Water to make up 1.000 ml.

After the usual procedures for stopping, hardening and waterwashing, thefilm is reexposed to white light and then treated at 20 C. for 12minutes with a developing solution of the following formulation:

N,N-diethyl-pphenylenediamine sulfate 5 g. Anhydrous sodium sulfite 2 gvSodium carbonate (monohydrate) 82 g.

Potassium bromide Water to make up 1,000 ml.

Thereafter, stopping, fixing, rinsing and bleaching are effected in theusual manner. Then the photographic film is washed with running waterfor 20 minutes and dried to obtain a cyancolored positive image whichhas an absorption maximum at 690 mp. and which is stable against light,heat and humidity.

EXAMPLE 3 N,N-diethyl-p-phenylenediamine sulfate 2.5 g. Anhydrous sodiumsulfate 2.0 g. Sodium carbonate (monohydrate) 82.0 g. Potassium bromide2.0 g.

Water to make up 1.000 ml.

Stopping and fixing are carried out in the usual manner. Afterwater-washing for l0-l5 minutes, this photographic film is treated for 5minutes in a bath of the following formulation:

Potassium ferricyanide Potassium bromide Water to make up L000 ml.

The film is washed with water for further 10 minutes and then dipped for5 minutes in a bath of the following formulation:

Sodium thiosult'ate Water to make up 1.000 ml.

After water-washing and drying, a cyan-colored image with an absorptionmaximum of 700 m is obtained which is stable against light, heat andhumidity.

What is claimed is:

l. A light-sensitive silver halide color-photographic material,containing a cyan coupler having the general formula:

wherein X is hydrogen atom, halogen atom, or sulfonic or sulfonategroup, Y is(Cl-l -,or CH -CH(CH and R is on an aliphatic hydrocarbonradical of eight to 20 carbon atoms. I

2. A light-sensitive silver halide color-photographic materialCONHCH,-CH,CH NHC OCH,C H-C1gHz5 as claimed in claim 1, wherein saidcyan coupler is: C 0H OH v C0NHCHzCHg-CH2NHCOCH2-CHC13H37 I 00H 5. Alight-sensitive silver halide color-photographic material as claimed inclaim 1, wherein said cyan coupler is:

OH 3. A light-sensitive silver halide color-photographic material I asclaimed in claim 1, wherein said cyan coupler is: c0 CH NHc0 cH,-CH-G,H

5 CH; O O H O CHPNH C Hr CHE 6. light-sensitive silver halidecolor-photographic material as claimed in claim 1, wherein said cyancoupler is: C O OH I S OaNa V CONHCHg-?HNHCO CH CHC1QH33 CH; C O OH 4. Alight-sensitive silver halide color-photographic material I as claimedin claim 1, wherein said cyan coupler is: c

2. A light-sensitive silver halide color-photographic material as claimed in claim 1, wherein said cyan coupler is:
 3. A light-sensitive silver halide color-photographic material as claimed in claim 1, wherein said cyan coupler is:
 4. A light-sensitive silver halide color-photographic material as claimed in claim 1, wherein said cyan coupler is:
 5. A light-sensitive silver halide color-photographic material as claimed in claim 1, wherein said cyan coupler is:
 6. A light-sensitive silver halide color-photographic material as claimed in claim 1, wherein said cyan coupler is: 